Soy composite materials comprising an amino resin and methods of making the same

ABSTRACT

The present invention provides composite materials derived from aqueous binder compositions comprising defatted soy flour of no greater than 43 micron mesh particle size, polymer particles of at least one emulsion (co)polymer, one or more amino resin, and, optionally, one or more reducing sugar. Also provided are methods of making and using composite materials containing the binder compositions.

The present invention relates to composite materials and methods ofmaking the same. In particular, the present invention relates toflexible composite material comprising a substrate material and a curedor dried binder composition, wherein the cured or dried bindercomposition is produced from an aqueous binder composition comprisingdefatted soy flour as the major component, one or more emulsion(co)polymer, one or more amino resin, and, optionally, one or morereducing sugar; and methods for making the same. The composite materialsmay find use in flexible applications, for example, in glass mats forroofing shingles.

The preparation of composite materials, for example, fiber structures(e.g., non-woven fiber insulation) and shaped articles (e.g., fiberboardand chipboard) are conventionally made using urea-formaldehyde (UF)resins, phenol-formaldehyde (PF) resins, or phenol-formaldehyde resinsextended with urea (PFU). Commercial binders have generally beendesigned to afford a binder that when cured is substantially rigid. Forexample, in fiberglass insulation binders, the cured binder allows theinsulation to be compressed, but have rigidity that allows thecompressed insulation to recover substantially to its original shapeonce compressive forces are removed. Accordingly, the insulation may beshipped in a rolled, compressed state and unrolled before installationto release the compression, and allow a fluffy, heat-insulating mat tobe installed. Fiberglass non-wovens made with a binder consistingessentially of an amino resin, most commonly a urea formaldehyde resin,often are brittle. Moreover, the strength properties of the mats maydeteriorate appreciably subsequent to their preparation, especially whenthe mats are subjected to wet conditions. For other applications, knownrigid binders are undesirable. For thin fiberglass or polyester mats foruse in roofing, the mats are held together with a binder that allows themat to flex substantially after the binder is cured, and allows the endproduct containing the mat to flex well in use. For example, in roofingmat, the end roofing product may be impregnated or layered withasphaltic materials, and the resultant roofing product must retainflexibility to allow it to conform to the roof (e.g., bend over peaksand into valleys), and to allow the roofing material to expand andcontract with temperature fluctuations, without the mat itselffracturing because it is too brittle and lacks flexibility. For thisreason, UF resin binders have, on occasion, been modified by formulatingthe UF resin with cross-linkers and various catalyst systems or byfortifying the UF resin with latex (emulsion) polymer. Flexible glassmats of this type may find use in a variety of applications, includingroofing, flooring underlayments, filtration media, and buildingproducts. However, in view of the toxicity of formaldehyde, which is apossible carcinogen, it is desirable to minimize the use of aminoresins. In particular, manufacturers desire compositions comprising amajority component of a natural product or a material derived from anatural product.

Existing commercial binders used in composite materials contain acarboxylic acid polymer and a polyol that esterify and form a rigidthermoset when heat cured. However, these binders are not well suited toapplications that require some flexibility.

One objective of the present invention is to provide flexible compositematerials comprising a substrate material and a cured or dried bindercomposition, wherein the cured or dried binder composition is producedfrom an aqueous binder composition which comprises greater than 50 wt.%, based on binder composition solids, of a natural product or amaterial derived from a natural product, such as defatted soy flour.Natural products have previously been used including soy-based bindersused in wood composite structures. Soy isolate or soy concentrate wereused because these highly processed forms are largely water solubleunder proper pH conditions. However, both are prohibitively expensiveand have failed to gain any widespread use as binders for compositematerials. Further, whole ground soy bean and defatted soy flour areinsoluble in water and difficult to work with.

Composites of defatted soy flour or soy protein isolate withstyrene-butadiene latex are disclosed in “Characterization of DefattedSoy Flour and Elastomer Composites”, L. Jong, Journal of Applied PolymerScience, Vol. 98, 353-361 (2005). L. Jong compares defatted soy flourwith soy protein isolate when soy is blended into styrene-butadienerubber at 10%, 20% and 30% levels in studying the effect of soy as aminor component filler in styrene-butadiene rubbers.

U.S. Patent Application Publication No. 2008/0051539, to Kelly,discloses curable binder compositions comprising at least onepolycarboxy emulsion copolymer, at least one hydroxyamide crosslinkerhaving at least two hydroxy groups, and at least one extender selectedfrom the group consisting of a polysaccharide or a vegetable protein ormixtures thereof. Kelly discloses that vegetable protein can comprisedefatted soy flour. However, the binder compositions disclosed in Kellywould be less suitable for composite materials of the present inventionbecause, at suitable formulation solids levels of 10-25%, or higher, thehydroxyamides raise the viscosity of soy-based binders which may resultin poor application during wet-laid mat formation, producing tracks,streaks, or low binder weight (LOI).

The inventor has endeavored to find a solution to the problem ofproviding composite materials reinforced with an inexpensive thermosetbinder that retains both flexibility and strength after cure, and isprimarily comprised of a natural product or material derived from anatural product.

STATEMENT OF INVENTION

The present invention provides composite materials comprising: (a) asubstrate material; and, (b) a cured or dried binder compositionproduced from an aqueous binder composition comprising i) polymerparticles of at least one emulsion (co)polymer; ii) defatted soy flourof no greater than 43 micron mesh particle size; and iii) one or moreamino resin in an amount of no more than 49 wt. %, based on the bindercomposition solids; wherein the composite material comprises ≦40 wt. %cured or dried binder composition; and, further wherein the bindercomposition comprises from 51 wt. % to 95 wt. % defatted soy flour,based on the binder composition solids; as well as methods for makingthe same.

In one embodiment of the invention, the binder composition comprisesfrom 55 wt. % to 85 wt. % defatted soy flour, based on the bindercomposition solids.

In an embodiment of the invention, the binder composition furthercomprises one or more reducing sugar. In one such embodiment, thereducing sugar component of the aqueous binder composition is selectedfrom the group consisting of fructose, glyceraldehydes, lactose,arabinose, maltose, glucose, dextrose, xylose, and levulose.

In another embodiment of the invention, the emulsion (co)polymercomprises, in polymerized form, from 5% to 25% by weight, based on theweight of the (co)polymer, of one or more carboxy acid monomer, oranhydride thereof, or salt thereof.

In yet another embodiment of the invention, the emulsion (co)polymer iscomprised of from 0.1 to 5 weight percent, based on the weight of thecopolymer, of one or more multi-ethylenically unsaturated monomer, inpolymerized form. In one such embodiment, the multi-ethylenicallyunsaturated monomer comprises allylmethacrylate.

In yet still another embodiment of the invention, the defatted soy flourhas been subjected to conditions that denature its protein component orformulated to denature its protein content. In another embodiment of theinvention, the defatted soy flour is in the form of an aqueousdispersion.

In a different embodiment of the invention, the aqueous bindercomposition further comprises lignin or derivatives thereof, such aslignosulfonate.

In another different embodiment of the invention, the aqueous bindercomposition further comprises a thermally generated acid. In one suchembodiment, the thermally generated acid is an ammonium salt of aninorganic acid.

In still another different embodiment of the invention, the aqueousbinder composition further comprises sodium bisulfite or sodiummetabisulfite, preferably at a level of 0.1 to 1 weight percent, basedon the weight of the total binder.

In yet another different embodiment of the invention, the aqueous bindercomposition further comprises one or more crosslinking agent consistingessentially of glycerol, glycerol derivatives, diethanolamine,triethanolamine, pentaerythritol, hydroxy alkyl urea, urea, oxazoline,polyvinyl alcohol, metal ions, such as ions of zirconium or zinc, andmixtures thereof.

In yet still another different embodiment of the invention, thesubstrate material is selected from the group consisting of: polyestermat, glass reinforcing mat, or microglass based substrate material.

In another aspect, the present invention provides methods for producinga composite material, said method comprising: a) treating a substratewith an aqueous binder composition, b) removing excess bindercomposition from the substrate, and c) curing or drying the bindercomposition on the substrate; wherein the aqueous binder compositioncomprises: i) polymer particles of at least one emulsion (co)polymer;ii) defatted soy flour of no greater than 43 micron mesh particle size;iii) one or more amino resin in an amount of no more than 49 wt. %,based on the binder composition solids; and iv) optionally, one or morereducing sugar; wherein the composite material comprises ≦40 wt. % curedor dried binder composition; and further wherein the binder compositioncomprises from 51 wt. % to 95 wt. % defatted soy flour, based on thebinder composition solids.

In yet another aspect, the present invention provides compositematerials for use in applications selected from the group consisting of:roofing, flooring, carpet backing, window treatments, ceiling tiles,wall coverings, roving, printed circuit boards, battery separators,filter stock, tape stock, composite facers, and reinforcement scrim forcementitious or non-cementitious masonry coatings.

In yet still another aspect, the present invention provides compositematerials comprising: (a) a substrate material; and, (b) a cured ordried binder composition produced from an aqueous binder compositionconsisting essentially of: i) polymer particles of at least one emulsion(co)polymer; ii) defatted soy flour of no greater than 43 micron meshparticle size; iii) one or more amino resin in an amount of no more than49 wt. %, based on the binder composition solids; and iv) one or morereducing sugar; wherein the composite material comprises ≦40 wt. % curedor dried binder composition; and, further wherein the binder compositioncomprises from 51 wt. % to 95 wt. % defatted soy flour, based on thebinder composition solids.

In yet another aspect, the present invention provides a compositecomprising a random collection of glass or polyester fibers impregnatedwith an aqueous binder that includes a) 2 to 45 weight percent, based onthe weight of total binder, of an emulsion (co)polymer; b) 35 to 95weight percent, based on the weight of total binder, of defatted soyflour having a particle size of not greater than 43 μm; and c) 1 to 49weight percent, based on the weight of the total binder, of an aminoresin.

The binder may include one or more reducing sugars, one or more salts,including ammonium salts of an organic acid or bisulfite salts such assodium bisulfite.

In yet another aspect, the composite is cured.

In another aspect, the invention is a composite comprising a randomcollection of glass or polyester fibers impregnated with an aqueousbinder that includes a) 10 to 20 weight percent, based on the weight oftotal binder of a styrene-acrylic polycarboxy emulsion copolymercrosslinked with allyl methacrylate; b) 60 to 75 weight percent, basedon the weight of total binder, of defatted soy flour having a particlesize of not greater than 43 μm; c) 5 to 20 weight percent, based on theweight of the total binder, of a urea formaldehyde resin; d) 2 to 10weight percent, based on the weight of the total binder, of dextrose;and e) 0.1 to 1 weight percent, based on the weight of the total binder,of sodium bisulfite or sodium metabisulfite.

This invention provides flexible composites for use in, for example,fiberglass or polyester mats for roofing shingles.

Unless otherwise indicated, any term containing parentheses refers,alternatively, to the whole term as if no parentheses were present andthe term without that contained in the parentheses, and combinations ofeach alternative. Thus, the term (co)polymer refers to a homopolymer orcopolymer. Further, (meth)acrylic refers to any of acrylic, methacrylic,and mixtures thereof.

As used herein, unless otherwise indicated, the phrase “molecularweight” refers to the weight average molecular weight (Mw) of a polymeras measured by gel permeation chromatography (GPC). The system iscalibrated with standards of known molecular weight and composition tocorrelate elution time with molecular weight. The techniques of GPC arediscussed in detail in Modern Size Exclusion Chromatography, W. W. Yau,J. J Kirkland, D. D. Bly; Wiley-Interscience, 1979, and in A Guide toMaterials Characterization and Chemical Analysis, J. P. Sibilia; VCH,1988, p. 81-84. Unless otherwise indicated, molecular weights for thewater soluble (co)polymers are measured using polyacrylic acid standardsknown in the art, and molecular weights for emulsion copolymers aremeasured using polystyrene standards. The molecular weights reportedherein for Mw are in daltons.

As used herein, the phrase “alkyl” means any aliphatic alkyl grouphaving one or more carbon atoms, the alkyl group including n-alkyl,s-alkyl, i-alkyl, t-alkyl groups or cyclic aliphatics containing one ormore 5, 6 or seven member ring structures.

A “reducing sugar” herein is any sugar that, in alkaline solution, formsan aldehyde. This allows the sugar to act as a reducing agent.

The term “unsaturated carboxylic acid monomers” or “carboxy acidmonomers” includes, for example, (meth)acrylic acid, crotonic acid,itaconic acid, 2-methyl itaconic acid, α,β-methylene glutaric acid,monoalkyl fumarates, maleic monomers; anhydrides thereof and mixturesthereof. Maleic monomers include, for example, maleic acid, 2-methylmaleic acid, monoalkyl maleates, and maleic anhydride, and substitutedversions thereof.

The term “unsaturated sulfonic acid monomers”, or “sulfonic acidmonomers” includes, for example,2-(meth)acrylamido-2-methylpropanesulfonic acid and para-styrenesulfonic acid.

As used herein, the term “ammonium” includes, but is not limited to,⁺NH₄, ⁺NH₃R¹, ⁺NH₂R¹R², where R¹ and R² are each independently selected,and where R¹ and R² are selected from alkyl, cycloalkyl, alkenyl,cycloalkenyl, heterocyclyl, aryl, and heteroaryl. That is, the term“ammonium” includes “alkyl ammonium”.

As used herein, the phrase “aqueous” or “aqueous solvent” includes waterand mixtures composed substantially of water and water-misciblesolvents.

As used herein, “wt %”, “wt. %” or “wt. percent” means weight percent.

As used herein, the phrase “based on the total weight of binder solids”and “based on the binder composition solids” refers to weight amounts ofany given ingredient in comparison to the total weight amount of all thenon-water ingredients in the binder (e.g., emulsion copolymers, defattedsoy binder, soluble polyacids, reducing sugar, and other formulationingredients).

As used herein, unless otherwise indicated, the word “copolymer”includes, independently, copolymers, terpolymers, block copolymers,segmented copolymers, graft copolymers, and any mixture or combinationthereof.

As used herein, the phrase “emulsion (co)polymer” refers to a(co)polymer that has been prepared by emulsion polymerization.

As used herein, the phrases “(C₃-C₁₂)—” or “(C₃-C₆)—” and the like referto compounds containing 3 to 12 carbon atoms and 3 to 6 carbon atoms,respectively.

As used herein, mesh particle size refers to the particle size of amaterial that results from the sample passing through a sieve of thatmesh size. For example, defatted soy flour milled so that it passesthrough a 43 micron mesh (325 mesh) is referred to as having a 43 micronmesh particle size.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one skilled in the art. The endpoints of allranges directed to the same component or property are inclusive of theendpoint and independently combinable.

As used herein, unless otherwise indicated, the term “viscosity” refersto viscosity as measured on a DV-III Ultra LV Brookfield viscometer at 6rpm using spindle #31 with sample temperature maintained at a constant25° C.

Unless otherwise indicated, the term “Protein Dispersibility Index”(PDI) refers to a means of comparing the dispersibility of a protein inwater in which a sample of a soybean material is ground, mixed with aspecified quantity of water, and then blended at a specific rpm for aspecified time. The resulting mixture and whole soybean flour then havetheir protein nitrogen content measured using a combustion test, and thePDI is calculated as the percentage of the protein nitrogenconcentration in the mix divided by the percentage in the whole soybeanflour. A PDI of 100 therefore indicates total dispersibility of theprotein present in the soy flour. The total solubility of a given flourmay be less than the PDI, and is inversely proportional to thecarbohydrate content. The PDI can be affected, not only by the type ofsoybean used, but also by manufacturing processes; for example, heattreatment has been shown to lower the PDI.

According to the present invention, defatted soy flour comprises about51-95%, or 51-90% weight percent of the total solids in the binder,preferably 55-90%, or 55-85%, more preferably 60-85% or 60-80%, and mostpreferably 65-80%, or 65-75%, with the remainder being comprisedprimarily of one or more emulsion (co)polymer, one or more amino resin,and, optionally, one or more reducing sugar. Defatted soy flour assupplied is insoluble in water, but an aqueous dispersion can beobtained either by high shear grinding, preferably in the presence of adispersant, or by pre-cooking or denaturing the soy protein. Suitabledefatted soy flour starting materials may have PDI values of, forexample, 20, 70, and 90.

Suitable defatted soy flour materials may be commercially available orthey may be made from ground whole beans (including the hulls, oil,protein, carbohydrate, minerals, etc.), or meal (extracted or partiallyextracted). As used herein, “flour” includes within its scope defattedsoy flour, soy protein concentrate (partially processed flour containingapproximately 60-70% protein, less than about 0.5 wt. % oil andapproximately 10-20 wt. % carbohydrate), and soy protein isolate (highlyprocessed and substantially pure protein flour containing less thanabout 0.5 wt. % oil and less than about 5 wt. % carbohydrate). As usedherein, the term “defatted soy flour” refers to soy materialcontaining >20 wt. % carbohydrate, while still referring to a flourwhere the oil has been removed (“defatted”) to levels below 1.5 wt. %.

In the present invention, a soy flour having a mesh size of 43 microns(325 mesh) is preferred, and a mesh size of 400 or higher is mostpreferred. Larger particles are undesirable because the fiber mateffectively filters the large particles and captures them on the surfaceof the substrate. The desired particle size can be obtained by suchtechniques as rotapping, ball milling, hammer milling, or rotormilling.Milling techniques crush and further reduce the particle size of theas-supplied material for later use.

To provide a suitable soy-based binder, in a stable homogeneous aqueousdispersion of fine particle size defatted soy flour material at asuitable solids content (from 10% to 25% solids, or higher, in theaqueous dispersion), and at a stable viscosity that allows for facilestirring and transfer through pouring or pumping, the minimallyprocessed grades of soy flour cannot be simply stirred into water toproduce such a dispersion. The use of low shear pumps and blendingmixers fail to produce commercially useful dispersions. However,suitable dispersions of useful viscosities can be achieved by high sheargrinding, which may be provided by any suitable apparatus. Viscositiesof approximately 1,000 cps can be attained using a high shear grindingapparatus, such as by grinding using a high shear Cowles dissolver.Other suitable high speed shear apparatus include, but are not limitedto: (a) high speed shear impellers or pumps rotating at speeds in therange 1,000-3,500 rpm, preferably 2,000-3,500 rpm, (e.g. Tri-Blender byLadish Company, Tri-Clover Division); (b) homogenizers (e.g. Oakes Mixerby Oakes Machine Corp.); and (c) high speed agitators, mixers, orturbines (e.g. the “Likwifier” turbine mixer by Lanco and the mixers andaerators by “Lightnin” Co.). Preferably, one or more water-solublepolymer dispersing species is included in the high shear grindingprocess to attain lower viscosity ranges of approximately 400 to 1,000cps, preferably up to 600 cps, for the soy flour dispersions, therebyfacilitating handling and mixing. Slurries of higher PDI defatted soyflours exhibit much lower viscosities when ground under high shear inthe presence of such water soluble polymer dispersing species. Thedefatted soy flour may be prepared in the form of a slurry prior tocombination with the emulsion polymer. When prepared in this manner, theviscosity of the aqueous soy flour slurry is preferably from 100 to3,000 cps, more preferably 200 to 2,000 cps, or 200 to 1,000 cps, andeven more preferably 200 to 800 cps, or 200 to 600 cps.

Water soluble polymer dispersing species may be generated from at leastone anionic monomer. Some suitable anionic monomers are, for example,ethylenically unsaturated acid monomers, including, for example,ethylenically unsaturated carboxylic acid monomers, and sulfonic acidmonomers. The water soluble polymer dispersing species may optionallyinclude at least one cationic monomer. In some embodiments, the watersoluble polymer contains at least one polymerized unit from nonionicmonomers (i.e., a monomer that is neither a cationic monomer nor ananionic monomer). Some suitable nonionic monomers include, for example,ethylenically unsaturated nonionic compounds, including compounds withone or more double bond, such as olefins, substituted olefins(including, for example, vinyl halides and vinyl carboxylates), dienes,(meth)acrylates, substituted (meth)acrylates, (meth)acrylamide,substituted (meth)-acrylamides, styrene, substituted styrenes, andmixtures thereof. Further suitable water soluble polymers may bepolycarboxy addition (co)polymers which contain at least two carboxylicacid groups, anhydride groups, or salts thereof. Ethylenicallyunsaturated carboxylic acids may range in amount from about 1% to 100%,by weight, based on the weight of the water soluble polymer.

The water soluble polymer dispersing species may be made by anypolymerization method, including, for example, solution polymerization,bulk polymerization, heterogeneous phase polymerization (including, forexample, emulsion polymerization, suspension polymerization, dispersionpolymerization, and reverse-emulsion polymerization), and combinationsthereof, as is known in the art. The molecular weight of such watersoluble polymeric species may be controlled by the use of a chainregulator, for example, sulfur compounds, such as mercaptoethanol anddodecyl mercaptan. Typically, the amount of chain regulator, as apercentage by weight based on the total weight of all monomers used, is20% or less, more commonly 7% or less. The molecular weight of the watersoluble polymer is preferably from about 300 to about 100,000, or about1,000 to 100,000, more preferably 1,000 to 20,000, or 2,000 to 20,000,and even more preferably from 2,000 to 5,000, or from 2,000 to 3,000.For example, the water soluble polymer may be in the form of a solutionof the polycarboxy (co)polymer in an aqueous medium such as, forexample, a polyacrylic acid homopolymer or an alkali-soluble resin whichhas been solubilized in a basic medium. Many commercial dispersants andspecies of similar composition can function as the water solublepolymer. The polymers used as additives in these compositions can beneutralized with a base such as NH₄OH if desired. Suitable commercialdispersants include, for example, Acumer™ and Acusol™ 420N, availablefrom the Rohm and Haas Company (Philadelphia, Pa., USA). The one or morewater-soluble polymer species may be used in amounts ranging from0.1-5%, preferably 0.2-4%, and more preferably 0.5-3%, or 1-2%, based onthe weight of the polymeric active ingredient as a percentage of thetotal weight of the slurry, and functions as a dispersant for the soyflour particles in reducing the viscosity of the slurry. Preferably, thestabilized aqueous soy flour slurry comprises 10-60% defatted soy flour,preferably about 20%, based on the total weight of the slurry, theaqueous slurry being formed by high shear mixing on a Cowles dissolverin the presence of 1-2% of a water soluble polymer, such as Acusol™420N.

Alternatively, the soybean flour may be prepared by denaturing theprotein component of the soy flour, as is known to those skilled in theart, as described in, for example, U.S. Pat. No. 6,306,997. The defattedsoy flour may be pre-cooked prior to mixing with the emulsion copolymer;or neutralized with base before or after mixing with the emulsioncopolymer, or heated with chemical compounds which denature the proteincomponent of the soy flour. One method for preparing the soy flourslurry includes dissolving sodium bisulfite in water, adjusting the pHto from about 6.8 to 7.1 with sodium hydroxide, heating the solution tofrom about 45° C. to about 55° C., adding defoamer, and adding dry soyflour under conditions effective to produce the soy slurry. Preferably,the slurry is heated to about 50° C. Addition of sodium bisulfite duringpreparation of soy flour slurry partially depolymerizes the soy proteinby cleaving the disulfide linkages. Cleavage of disulfide bonds reducesthe viscosity of the soy slurry. Maintaining the soy flour slurry at theneutral pH and 50° C. obtains a higher solubility of soy flour andavoids protein gelation. Adding defoamers reduces foaming of the soyflour slurry, making preparation of the soy flour slurry easier tohandle. Preferred defoamers include cedarwood oil, Byk 024, Sigmaantifoam 204, pine oil, Pamolyn 200 (linoleic acid) or similar fattyacids, including unsaturated, monounsaturated, and polyunsaturated.Preparation of soy flour in this manner produces a slurry at a solidcontent as high as possible and at a viscosity manageable in thesubsequent resin formulation.

The aqueous binder compositions of the present invention comprise one ormore amino resin. Amino resins, such as urea formaldehyde resins, arewell known and widely commercially available. They are formed, forexample, from the reaction of urea and formaldehyde to form compoundscontaining methylol groups, which subsequently under the application ofheat, with or without catalysts, react further, or condense, or cure toform polymers. The methylol groups in the resin are known to react withactive hydrogen groups such as other methylol groups to form ether ormethylene groups thereby forming polymeric structures. Such polymericstructures are generally brittle and nonwovens containing such resins assole binders tend to be relatively inflexible. An example of acommercially available urea formaldehyde resin is SU-100 (HexionSpecialty Chemicals, Columbus, Ohio, USA).

The amino resin component of this invention, for example, may be atleast one amino resin selected from the group consisting of melamineformaldehyde resin, urea formaldehyde resin, guanamine formaldehyderesin, benzoguanamine formaldehyde resin and aceto-guanamineformaldehyde resin, and the like, as is known in the art. Otheramine-bearing materials may be used to form analogous amino resins bysimilar techniques, including glycoluril, thiourea, aniline, andparatoluene sulfonamide. Preferred are urea-formaldehyde (UF) resins.The amino resin may also comprise a polymer modifier, such as a(meth)acrylic (co)polymer, a polyvinylalcohol (co)polymer, astyrene-(meth)acrylic copolymer, a styrene-(meth)acrylic acid copolymer,a styrene-butadiene copolymer, a styrene-maleic anhydride copolymer, ora copolymer comprising styrene, maleic anhydride, and a (meth)acrylicacid, or a copolymer comprising styrene, maleic anhydride, and a(meth)acrylate. An example of a modified UF resin is FG-705 (HexionSpecialty Chemicals, Columbus, Ohio, USA). The amino resin component maybe present at levels from 1 wt. %, based on binder composition solids,or from 5 wt. %, and may range from up to 49 wt. %, preferably up to 40wt. %, more preferably up to 20 wt. %.

In an embodiment, the aqueous binder composition of the presentinvention comprises at least one reducing sugar. A reducing sugar hereinis any sugar that, in alkaline solution, forms an aldehyde. This allowsthe sugar to act as a reducing agent, for example in a Maillard reactionwith an amine source. A sugar may be a reducing sugar when its anomericcarbon (the carbon linked to two oxygen atoms) is in the free form.Sugars may occur in a chain as well as a ring structure and it ispossible to have an equilibrium between these two forms. It should benoted that some keto sugars are also reducing sugars because some can beconverted to an aldehyde via a series of tautomeric shifts to migratethe carbonyl to the end of the chain.

Reducing sugars include all monosaccharides, whether aldose (containingan aldehyde) or ketose (containing a ketone). Accordingly, the reducingsugar component of the present invention may be a monosaccharide in itsaldose or ketose form, including a triose, a tetrose, a pentose, ahexose, or a heptose. Most disaccharides are also reducing sugars.Reducing sugars include glucose, fructose, glyceraldehydes, lactose,arabinose, xylose, and maltose. Other natural or synthetic stereoisomersor optical isomers of reducing sugars may also be useful as the reducingsugar component of the aqueous binder composition; for example,dextrose, which is one of the optical isomers of glucose. The reducingsugar component of the aqueous binder composition optionally may besubstituted, for example with hydroxy, halo, alkyl, alkoxy, or othersubstituent groups.

Dextrose has been found to be particularly suitable. In one embodiment,a high dextrose content syrup (greater than 30% dextrose) is used as thereducing sugar component. In such syrups, the higher the dextrosecontent, the better; syrups with 97%, or greater, dextrose content arecommercially available, for example ADM 97/71 corn syrup, from ArcherDaniels Midland Company (Decatur, Ill., USA).

The reducing sugar may comprise from 3%, or from 5%, or from 7%, up to30%, or up to 25%, or up to 20% by weight of solids as a percent of thetotal solids in the binder; preferably the reducing sugar comprises from5%, or from 7%, up to 20%, or up to 15%, by weight of solids as apercent of the total solids in the binder; and most preferably from5-15%, or 8-12%.

The emulsion (co)polymer used in the binder of the composite materialmay comprise, as copolymerized units, ethylenically unsaturated monomersincluding (meth)acrylic ester monomers such as methyl acrylate, ethylacrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, laurylacrylate, methyl methacrylate, butyl methacrylate, isodecylmethacrylate, lauryl methacrylate, hydroxyalkyl (meth)acrylate monomerssuch as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate,1-methyl-2-hydroxyethyl (meth)acrylate, and N,N-dimethylaminoethyl(meth)acrylate; as well as the related amides and nitriles, such as(meth)acrylamide or substituted (meth)acrylamides, and acrylonitrile ormethacrylonitrile. Other ethylenically-unsaturated nonionic monomerswhich may be incorporated into the polymer include vinylaromaticcompounds, such as styrene or substituted styrenes; ethylvinylbenzene,vinylnaphthalene, vinylxylenes, vinyltoluenes, and the like; butadiene;vinyl acetate, vinyl butyrate and other vinyl esters; vinyl monomerssuch as vinyl alcohol, vinyl ethers, vinyl chloride, vinyl benzophenone,vinylidene chloride, and the like; allyl ethers; N-vinyl pyrrolidinone;and olefins. Other suitable emulsion (co)polymers may includestyrene-acrylic latexes, or all-acrylic latexes, or styrene-butadiene orstyrene-acrylonitrile-butadiene latexes. The emulsion (co)polymer usedin the binder of the composite material preferably comprises about2-45%, or 5-45% weight percent of the total solids in the binder,preferably 5-40%, or 10-40%, more preferably 5-25% or 10-25%, and mostpreferably 15-25%.

The emulsion copolymer used in the binder of the composite material mayinclude, as polymerized units, ethylenically unsaturated carboxylic acidmonomers, or hydroxy monomers, such as (meth)acrylic acid andhydroxyethyl-(meth)acrylate. Acrylic acid is the preferred carboxylicacid monomer. As used herein, the term, “as polymerized units” or “ascopolymerized units” refers to the repeating units formed by thepolymerization of the monomer referred to. Thus, an emulsion copolymerthat is said to include, as polymerized units, acrylic acid, will havethe following repeating units:

In a preferred embodiment the emulsion copolymer used in the binder ofthe composite material includes, as copolymerized units, from 5% to 40%,or 5% to 30%, or 5% to 25%, or 5% to 15%, preferably from 10% to 30%, or10% to 20%, or 12% to 20%, most preferably 12% to 17% or 14% to 17%, byweight based on the weight of the emulsion copolymer solids, of acarboxylic acid monomer or hydroxy monomer, such as (meth)acrylic acidand hydroxyethyl (meth)acrylate.

In one embodiment, the latex emulsion (co)polymer of this inventioncomprises one or more copolymerized multi-ethylenically unsaturatedmonomers such as, for example, allyl methacrylate (ALMA), allylacrylate, diallyl phthalate, 1,4-butylene glycol dimethacrylate,1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate,butadiene, trimethylolpropane triacrylate (TMPTA) and divinyl benzene.Of these, ALMA, divinylbenzene (DVB), diallyl phthalate, 1,4-butyleneglycol dimethacrylate, and 1,6-hexanediol diacrylate are preferred. ALMAis the most preferred. The multi-ethylenically unsaturated monomer canbe effectively employed at levels as low as 0.1%, by weight based on theweight of the copolymer, preferably from 0.1 to 10%, or 0.1 to 5%, morepreferably from 0.1 to 4%, or 0.2 to 4%, and most preferably from 0.1 to3%, or 0.2 to 3%, or 0.25 to 3%, or 1.0 to 3%, by weight based on theweight of the copolymer.

The polymer particles of the latex emulsion (co)polymer may optionallycontain crosslinking groups that are capable of forming chemical bondsduring and after drying of the aqueous polymer composition. Thecrosslinking groups may be present in the polymer particles aspolymerized ethylenically unsaturated monomers containing pendantcrosslinking groups, referred to herein as “crosslinking monomers”.Crosslinking monomers may include, for example, monomers havingalkoxymethyl amide groups, such as, N-methylolacrylamide,N-methylolmethacrylamide, n-butoxymethyl acrylamide, n-butoxymethylmethacrylamide. Such monomers may be employed at levels of 0.1-10 wt. %.

Suitable chain transfer agents such as mercaptans, polymercaptans, andhalogen compounds can be used in the polymerization mixture in order tomoderate the molecular weight of the emulsion copolymer composition, inthe amount of from 0% to 10% by weight, based on the weight of theemulsion copolymer.

Preferably, the emulsion copolymer used in this invention has a Tg ofbetween −20° C. to 35° C., preferably −10° C. to 20° C., as measured bydifferential scanning calorimetry per ASTM 3418/82, midpointtemperature; cell calibration using an indium reference for temperatureand enthalpy.

The emulsion copolymer used in this invention has weight averagemolecular weight of between 5,000 to 2,000,000, preferably between20,000 and 1,000,000. For applications requiring high performance atelevated temperatures, the emulsion copolymer most preferably has aweight average molecular weight of 100,000 to 1,000,000, however, forsome room temperature applications, the molecular weight is mostpreferably between 30,000 and 600,000.

The binder of this invention may further include a soluble addition(co)polymer, containing at least two carboxylic acid groups, anhydridegroups, or salts thereof, referred to herein as a “polyacid”.Ethylenically unsaturated carboxylic acids, at a level of at least 70%by weight based on the weight of the soluble addition (co)polymer, maybe used. Additional ethylenically unsaturated monomer may includeacrylic ester monomers, including methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl acrylate, etc. Thepolyacid may have a molecular weight from about 1,000 to 150,000, andmay be used at a level from 0%-30% by weight based on the total weightof solids of the emulsion copolymer.

In one embodiment of the invention, the composition further contains atleast one low molecular weight polybasic carboxylic acid, anhydride orsalt thereof having a molecular weight of 1000 or less, preferably 500or less, and most preferably 200 or less. “Polybasic” means having atleast two reactive acid or anhydride functional groups. Examples ofsuitable low molecular weight polybasic carboxylic acids and anhydridesinclude, for example, maleic acid, maleic anhydride, fumaric acid,succinic acid, succinic anhydride, sebacic acid, azelaic acid, adipicacid, citric acid, glutaric acid, tartaric acid, itaconic acid,trimellitic acid, hemimellitic acid, trimesic acid, tricarballytic acid,1,2,3,4-butanetetracarboxylic acid, pyromellitic acid, oligomers ofcarboxylic acid, and the like. When used, preferably, the low molecularweight polybasic carboxylic acid, anhydride or salt thereof ispre-cooked with the soy or lignosulfonate, prior to mixing with theemulsion copolymer. Most preferably, citric acid is used as thepolybasic acid.

In another embodiment of this invention, the binder composition furthercomprises constituents for preserving the soy flour such as ascorbicacid, citric acid, or salts thereof; other preservatives may includesodium or potassium carbonate, sulfite, bisulfite or metabisulfite orcombinations thereof.

In another embodiment of this invention, the binder composition furthercomprises one or more crosslinking agent. The crosslinking agent may beadded at a level of 0.3 to 100 equivalents based on equivalents of acidof the emulsion copolymer, and may be selected from, for example,polyols, polyamines or metal ions, where the polyol contains two or morehydroxy groups, and the polyamine contains two or more amine groups.Species containing both hydroxy and amine functionality can also beused. Suitable crosslinkers include glycerol, glycerol derivatives,diethanolamine, triethanolamine, pentaerythritol, hydroxy alkyl urea,urea, oxazoline, polyvinyl alcohol, as well as metal ions such as ionsof zirconium or zinc. The compositions should not includehydroxyalkylamides.

In yet another embodiment of this invention, the binder compositioncomprises a phosphorous-containing accelerator such as those disclosedin U.S. Pat. No. 6,136,916. Preferably, the accelerator is selected fromthe group consisting of sodium hypophosphite, sodium phosphite, or amixture thereof. The phosphorous-containing accelerator can also be anoligomer bearing phosphorous-containing groups such as, for example, anoligomer of acrylic acid formed in the presence of sodium hypophosphiteby addition polymerization, but a separate compound from any solublepolyacid polymer serving as part of the binder of the curablecomposition of the present invention. Amounts of the one or morephosphorous-containing accelerator may range from 0 wt. % to 40 wt. %,based on the total weight of binder solids (combined soy, emulsioncopolymer, and reducing sugar solids), such as 0.1 wt. % or more, and upto 25 wt. %, or up to 20 wt. %, or, preferably, up to 15 wt. %, and,more preferably, up to 12 wt. %, all wt. % based on the total weight ofbinder solids. When the phosphorous-containing accelerator comprisespart of an addition (co)polymer or (co)oligomer, the wt. % of thephosphorous-containing accelerator is determined by wt % of theaccelerator charged to the reactor as a fraction of the total solids.Other catalyst systems optionally may be used, such as Lewis acids orbases.

In yet still another embodiment, the curable compositions may optionallycontain one or more strong acids, wherein the strong acid has a pKa of≦3.0. The composition may contain up to 0.2 equivalents of a strongacid, relative to the equivalents of total carboxylic acid from theemulsion polymer and the optional soluble polymer, such as from 0.01 to0.18 equivalents. The strong acid may be a mineral acid, such as, forexample, sulfuric acid, or an organic acid, such as, for example, asulfonic acid. Mineral acids are preferred. The amount of acid, and themethod of addition, is regulated such that the emulsion copolymer is notcoagulated or otherwise adversely affected.

In an embodiment, the curable compositions comprise a thermallygenerated acid catalyst. Ammonium salts of inorganic acids may besuitable; for example, ammonium salts of sulfuric acid, or nitric acid,or hydrochloric acid, or phosphoric acid, or phosphorous acid amongothers. Such salts may be mono-basic, or dibasic, or polybasic dependingon the acid. For example, phosphoric acid (H₃PO₄) can have three acidicprotons. Suitable examples include ammonium sulfate, ammoniumpersulfate, ammonium chloride, ammonium nitrate, ammonium phosphate,ammonium hydrogen phosphate, ammonium para-toluene sulfonate, andammonium naphthalene disulfonate. Such species may be added to theformulation. The term “ammonium” includes “alkyl ammonium”. The ammoniumsalt may be present at a level of 1-10 weight percent based on solids asa percentage of the total solids in the binder. Preferably, the ammoniumsalt is present at a level of from 1%, or from 2%, up to a level of 10%,or up to 8%; and, most preferably, is at a level of from 2% up to 5%based on solids as a percentage of the total solids in the binder.

Alternatively, the thermally generated acid may be incorporated as afunctional group within one of the binder components; for example, theemulsion polymer may comprise one or more monomer units which include anacid functional group that may be liberated from the polymer during thecure of the composite. Monomers of this type include2-acrylamido-2-propane sulfonic acid (AMPS), para-styrene sulfonic acid,and other sulfonic acid monomers. The monomer of this type may beincorporated into the polymer by polymerizing the free acid form andthen neutralizing with ammonia after the polymer has been formed.

In a particularly preferred embodiment, the composite material comprisesa binder composition of i) approximately 51-90% by weight, preferably60-75%, based on the total weight of binder solids, of defatted soyflour; ii) approximately 10-20% by weight of an acrylic orstyrene-acrylic polycarboxy emulsion copolymer; iii) approximately 5-20%by weight of an amino resin, preferably a UF resin; and iv) optionally,approximately 2-10% by weight of a reducing sugar, such as dextrose orfructose. Optionally, the further addition of other additives, as shownin the Examples, may be advantageous. For each component, the percentageby weight is the percent weight of solids of the component as apercentage of the total weight of solids of the binder. Compositesamples 2-8 of Table 14, below, are representative of this embodiment.

The binder of this invention can contain, in addition, conventionaltreatment components such as, for example, emulsifiers; pigments;fillers or extenders, such as lignosulfonate; anti-migration aids;curing agents; coalescents; surfactants, particularly nonionicsurfactants; spreading agents; mineral oil dust suppressing agents;preservatives or biocides, such as isothiazolones, phenolics, or organicacids; plasticizers; organosilanes; anti-foaming agents such asdimethicones, silicone oils and ethoxylated nonionics; corrosioninhibitors, particularly corrosion inhibitors effective at pH<4 such asthioureas, oxalates, and chromates; colorants; antistatic agents;lubricants; waxes; anti-oxidants; coupling agents such as silanes,particularly Silquest™ A-187 (manufactured by GE Silicones—OSiSpecialties, Wilton, Conn.); polymers not of the present invention; andwaterproofing agents such as silicones and emulsion polymers,particularly hydrophobic emulsion polymers containing, as copolymerizedunits, greater than 30% by weight, based on the weight of the emulsionpolymer solids, ethylenically-unsaturated acrylic monomer containing aC5 or greater alkyl group. These components may be simply admixed withthe dispersed soy and emulsion (co)polymer dispersion.

The inventive composite material comprises a substrate material chosenfrom fibers, slivers, chips, particles, and combinations thereof, and abinder composition comprising one or more emulsion copolymer, defattedsoy flour, and one or more reducing sugar. Suitable fibers may be chosenfrom natural fibers (e.g., sisal, jute, hemp, flax, cotton, coconutfibers, banana fibers); animal fibers (e.g., wool, hair); plastic fibers(e.g., polypropylene fibers, polyethylene fibers, polyvinyl chloridefibers, polyester fibers, such as rayon, polyamide fibers,polyacrylonitrile fibers, polylactic acid fibers, polycaprolactonefibers, and bi-component fiber comprising two or more fiber-formingpolymers such as polypropylene and polyethylene terephthalate); glassfibers; glass wool; mineral fibers; mineral wool; synthetic inorganicfibers (e.g., aramid fibers, carbon fibers); and combinations thereof.In some embodiments of the invention, the substrate material is selectedfrom the group consisting of polyester mat, glass reinforcing mat, ormicroglass based substrate material. Preferably, the fibers are glassfibers or polyester fibers.

In one embodiment of the present invention, the fibers are chosen fromheat resistant fibers, such as mineral fibers, aramid fibers, ceramicfibers, metal fibers, carbon fibers, polyimide fibers, polyester fibers,glass fibers, glass wool, mineral wool and combinations thereof.Heat-resistant non-wovens may also contain fibers which are not inthemselves heat-resistant such as, for example, nylon fibers, andsuperabsorbent fibers, in so far as or in amounts such that they do notmaterially adversely affect the performance of the substrate. Suitablefibers, slivers, chips, particles or particulate matter and combinationsthereof, may be chosen from any comprised of metal, metal oxides,plastic, minerals, glass, paper, cardboard, and combinations thereof. Inone embodiment, the fibers, slivers, chips, particles or particulatematter and combinations thereof are heat resistant. In anotherembodiment, methods of the present invention comprise: treating asubstrate with a wet binder composition, followed by removing excessbinder composition from the substrate, and curing or drying the bindercomposition on the substrate. The binder can be applied to the substrateby any suitable means including, for example, air or airless spraying,padding, saturating, roll coating, curtain coating, beater deposition,coagulation, or dip and squeeze application. To remove excess binder,the resultant saturated wet web may be run over one or more vacuum boxesto remove enough binder to achieve the desired binder content in themat. Preferably, the binder is applied to the web on a moving screen.The binder level in the inventive mats can range from about 10 to about40 wt. percent of the finished dry mat, preferably about 15 to about 30wt. percent and, most preferably, from about 20 to about 30 wt. percent,such as about 25+/−3 wt. percent. The binder composition is curable ordried by the application of heat.

The binders of this invention are useful to bind non-woven webs, amongother things. “Non-woven web(s)” refers to any article or sheet-likeform made from natural and/or synthetic fibers, including porous filmsprepared by the action of chemical or mechanical processing (e.g.,apertured films), paper and paper products. One skilled in the artunderstands that formation of some order occurs during the web formingprocess (primarily in the machine direction). Manufacturing processesfor making non-woven webs are well known in the art. These include, forexample, wet-laid, air-laid (dry laid), spunbond, spunlace, meltblownand needle punch. Particularly suitable webs will have a base weight(i.e., the weight of the web before any coating or treatments areapplied) of less than about 100 grams per square meter (gsm). In anotheraspect the webs will have a base weight of less than about 20 gsm.

The soy flour may be slurried in water and mixed with other binderingredients and then heated or cooked before application onto thesubstrate, and any other binder ingredients not added to the slurryduring this heating or cooking process may be either mixed with theheated or cooked soy flour slurry before or after application of the soybinder to the substrate. Preferably, a jet cooker is employed where thesoy is cooked and spray-dried onto the substrate.

In drying (if applied in aqueous form) and curing the bindercompositions, the duration, and temperature of heating, will affect therate of drying and the ease of processing or handling the treatedsubstrate, as well as the property development of the resultingcomposite. Suitable heat treatment at 100° C. or more, and up to 400°C., may be maintained for from 3 seconds to 15 minutes. Preferably, heattreatment temperatures range 150° C. or higher; such preferred heattreatment temperatures may range up to 225° C., or, more preferably, upto 200° C. or, when using one or more phosphorous-containingaccelerator, up to 150° C.

Drying and curing can be done in two or more distinct steps, if desired.For example, the curable composition can be first heated at temperaturesand for times sufficient to substantially dry, but not to substantiallycure the composition, followed by heating for a second time, at highertemperatures and/or for longer periods of time, to effect curing. Suchprocedures, referred to as “B-staging,” can be used to providebinder-treated non-wovens, for example, in roll form, which can be curedlater, with or without forming or molding into a particularconfiguration, concurrent with the curing process.

Some non-woven fabrics are used at temperatures substantially higherthan ambient temperature such as, for example, glass fiber-containingnon-woven fabrics which are impregnated with a hot asphaltic compositionpursuant to making roofing shingles or roll roofing material. When anon-woven fabric is contacted with a hot asphaltic composition attemperatures of from 150° C. to 250° C., the non-woven fabric can sag,shrink, or otherwise become distorted. Therefore, non-woven fabricswhich incorporate a curable composition should substantially retain theproperties contributed by the cured aqueous binder composition such as,for example, tensile strength. In addition, the cured composition shouldnot substantially detract from essential non-woven fabriccharacteristics, as would be the case, for example, if the curedcomposition were too rigid or brittle or became sticky under processingconditions. The composites described herein find utility in many variedapplications, particularly in glass mats for roofing shingles and glassmats for flooring.

EXAMPLES

These examples illustrate specific binder compositions of this inventionand ones that compare to such compositions.

The following abbreviations are used in the Examples:

-   SLS—sodium lauryl sulfate-   MMA—methyl methacrylate-   BA—butyl acrylate-   EA—ethyl acrylate-   ALMA—allyl methacrylate-   AA—acrylic acid-   MAA—methacrylic acid-   MOA—methylol acrylamide-   STY—styrene-   DI water—deionized water

The preparations and test procedures are carried out at room temperatureand standard pressure unless otherwise indicated.

Examples 1-6 Emulsion Copolymer Synthesis

A 5-liter round-bottom flask equipped with a paddle stirrer,thermocouple, nitrogen inlet, and reflux condenser was charged with876.4 grams of deionized water, 24.2 grams of sodium hypophosphitemonohydrate, 28.5 grams of a sodium lauryl ether sulfate surfactantsolution (30%), 3.1 grams of sodium hydroxide, and 0.058 grams of aninhibitor. The mixture was heated to 79° C.

For Example 1, a monomer emulsion was prepared using 459.7 grams ofdeionized water, 89.2 grams of a sodium lauryl ether sulfate surfactantsolution (30%), 553.9 grams of butyl acrylate, 969.7 grams of styrene,and 268.9 grams of acrylic acid. A 97.0 gram aliquot of this monomeremulsion was added to the reaction flask, with stirring, followed by asolution of 7.4 grams of ammonium persulfate dissolved in 33.3 grams ofdeionized water. After an exotherm and while maintaining a reactiontemperature of 85° C., the monomer emulsion and a separate solution of7.4 grams of ammonium persulfate in 156.9 grams of deionized water weregradually added over a total time of 130 minutes. After these additionswere complete a solution of 42.6 grams of sodium hydroxide dissolved in397.4 grams deionized water was added. A solution of 0.022 grams offerrous sulfate heptahydrate in 4.8 grams deionized water and a solutionof 0.022 grams of ethylene diamine tetraacetate, tetra sodium salt,dissolved in 4.8 grams of deionized water was added to the reactionmixture. A solution of 7.9 grams of aqueous tert-butylhydroperoxide(70%) diluted with 31.2 grams deionized water and a solution of 5.3grams of sodium bisulfite dissolved in 62.8 grams of deionized waterwere gradually added to the reaction mixture. After a 15 minute hold, asolution of 7.9 grams of aqueous tert-butylhydroperoxide (70%) dilutedwith 31.2 grams deionized water and a solution of 5.3 grams of sodiumbisulfite dissolved in 62.8 grams of deionized water were graduallyadded to the reaction mixture. After addition of these solutions wascomplete, 47.6 grams of deionized water was added, and the reactionmixture was cooled to room temperature. When the reaction mixture wascool, a biocide was added and the latex was filtered through a 100 meshsieve. Examples 2-6 followed the same procedure, but with the monomeremulsions prepared as shown in Table 1.

The resulting latexes had a solids content of roughly 46.0%. Theemulsion copolymers of Example 1-6 had Tg as shown in Table 1.

TABLE 1 Monomer Emulsion Recipes for Latex Samples 1-6 (weights ingrams), and Copolymer Tg Example Example Example Example Example Example1 2 3 4 5 6 Deionized water 459.7 510.0 456.8 456.8 456.8 510.0 Sodiumlauryl ether 89.2 90.7 88.7 88.6 113.4 90.7 sulfate surfactant (30%)Butyl acrylate 553.9 953.3 1072.3 1072.3 1021.5 948.7 Styrene 969.7596.1 423.9 388.3 715.13 575.0 Acrylic acid 268.9 273.3 267.2 267.226.72 32.1 Allyl methacrylate 0.0 0.0 17.8 53.4 17.81 18.1 Copolymer Tg(° C.) 55 20 10 10 10 10

Example 7 Emulsion Copolymer Synthesis

A 2-liter, four necked round bottom flask, equipped with a condenser,thermocouple and overhead stirring, was loaded with a mixture of 405.0 gof deionized water, 105.0 g of acrylic latex of particle diameter 58 nmand 3.0 g of ammonium persulfate at 85° C. A monomer emulsion wasprepared using 125.0 grams of deionized water, 20.0 grams of a sodiumlauryl ether sulfate surfactant solution (30%), 258.0 grams of butylacrylate, 282.0 grams of methyl methacrylate, and 60.0 grams of acrylicacid. With the initial charge stirring at 85° C. the monomer emulsionand a solution of 3.0 g of ammonium persulfate in 66.0 g of deionizedwater were gradually added to the reaction flask over 120 minutes whilemaintaining the temperature at 85-87° C. After the addition of themonomer emulsion and ammonium persulfate solution was complete thereaction mixture was held at 85° C. for 15 minutes. The reaction flaskwas then cooled to 70° C. A solution of 1.40 g of 0.15% ferrous sulfateheptahydrate (aq.) was added with 10.0 g of deionized water. As thereaction mixture cooled a solution, of 1.0 g of isoascorbic acid in 10.0g of deionized water and a solution of 1.40 g of tert-butylhydroperoxide (70%) in 10.0 g of deionized water gradually added over 30minutes. The reaction mixture was then allowed to cool to below 30° C.and was filtered. The resulting latex had a solids content ofapproximately 46% and the copolymer had a Tg of 30° C.

Example 8 Preparation of Aqueous Admixture of Urea Formaldehyde (UF)Resin and Latex Emulsion Polymer

The comparative Sample 23, in Table 2 and 3 below, is an aqueousadmixture of UF resin FG-472× as a majority component and a latexemulsion copolymer Polymer B (Table 2), as follows: an aqueous admixturewith a UF/latex blend weight ratio of 9:1, at 20% solids, i.e. 9 weightparts UF resin solids per 1 part latex solids in 40 parts of water, isprepared.

In Table 2 and 3 below, comparative binders Samples 2-4 comprise UFresin alone (SU-100 or FG-472X, from Hexion Specialty Chemicals,Columbus, Ohio, USA). These control samples demonstrate the propertiesof the UF resin without any latex polymer modifier.

Example 9 Preparation of Aqueous Slurry of Defatted Soy Flour

A stable aqueous soy flour slurry comprising 20% defatted soy flour,based on the total weight of the slurry, is used in Examples 13-14unless otherwise indicated. The aqueous soy flour slurry used hereinemploys a soy flour of particle size equal to or smaller than thatcorresponding to 43 micron mesh particle size (325 mesh), and the slurryis formed by high shear mixing on a Cowles dissolver in the presence of1-2%, based on the weight of the polymeric active ingredient as apercentage of the total weight of the slurry, of a water solublepolymer, such as Acusol™ 420N. The latter is available from the Rohm andHaas Company (Philadelphia, Pa., USA). Acusol™ is a trademark of theRohm and Haas Company (Philadelphia, Pa., USA). This type of slurry isstable to settling, has a viscosity that is convenient for use,approximately 400-600 cps, and has minimal viscosity drift.

Example 10 Procedure for Denaturing Defatted Soy Flour

An aqueous slurry of defatted soybean flour, which contains about 54percent protein, 30 percent carbohydrates, 6 percent ash, and 10 percentmoisture, was prepared by dissolving in 250 ml water 1.25 g sodiumbisulfite (NaHSO₃) for each 100 grams of moisture-free soy flour to beadded. The pH was then adjusted to neutral with 50% aqueous sodiumhydroxide (NaOH) solution. The solution was heated to and maintained at50° C., followed by the addition of 1.0 g Byk 024, available from BYKChemie USA (Wallingford, Conn., USA). Subsequently, 100 grams of dry soyflour was slowly added with vigorous stirring, resulting in a viscousbut smooth and homogenous slurry. Again, the soy flour used has aparticle size equal to or smaller than that corresponding to 43 micronmesh particle size (325 mesh).

Alternative methods to denature the soy protein were explored, usingsodium hydroxide solution alone, or using sodium carbonate (see Table2). However, the combination of sodium hydroxide and sodium bisulfite ispreferred for ease of handling.

For the embodiment that contemplates addition of a polybasic carboxylicacid, anhydride or salt thereof, anhydrous citric acid (11.1 grams) isweighed into the same container along with the defatted soy flour (100.0grams), and the dry mixture is then added to the stirring water securedin the heated water bath. The procedure is otherwise as described above.This embodiment can also be adapted for use with the aqueous soy flourslurry described in Example 9 above, employing the procedure andcorresponding ratio of polybasic carboxylic acid (or anhydride, or saltthereof) used therein.

Example 11 Glass Mat Preparation Procedure and Test Procedures

To prepare the mats used in the examples that follow, glass fibernon-woven handsheets are prepared with Johns Manville 137 Standard, 3.2cm (1¼ inch) length, sized glass chop using approximately 7.6 grams ofglass fiber per sheet (0.82 kg per 9.3 square meters; 1.8 pounds per 100square feet). The glass fiber is dispersed in water using SUPERFLOC™A-1883 RS (Cytec Industries Incorporated, West Paterson, N.J., USA), ananionic polyacrylamide water-in-oil emulsion, and RHODAMEEN™ VP-532 SPB(Rhodia Chemical Company, Cranbury, N.J., USA), an ethoxylated fattyamine cationic dispersing agent. Handsheets are formed in a Williams(Williams Apparatus Company, Watertown, N.Y., USA) handsheet mold. Thewet sheets are transferred to a vacuum station and de-watered. Theaqueous binder compositions described below are prepared and each isapplied to a de-watered sheet and the excess is vacuumed off. The sheetsare dried/cured in a forced air oven for 2½ minutes at 200° C. Thebinder amount on the samples is 21% LOI (loss on ignition).

Determination of LOI (Loss On Ignition)

A 6.4 cm by 7.6 cm (2.5 inch by 3 inch) piece of dried/cured fiberglassmat was cut. The sample was weighed and then placed in a muffle furnaceat 650° C. for 2 minutes. The sample was removed and then reweighed. %LOI was calculated using the equation:

%LOI=(weight before burning−weight after burning)×100/weight beforeburning.

Tensile Strength Testing

Handsheets are cut into 2.54 cm by 12.7 cm (1 inch by 5 inch) strips fortensile testing and cut for tear testing. Tensile testing is performedon seven strips from each sample using a Thwing-Albert Intellect 500tensile tester (Thwing-Albert Instrument Co., West Berlin, N.J., USA)with a 90.7 kg (200 lb.) cell, 2.54 cm/min (1 inch/min) jaw speed, 20%sensitivity, and a 7.6 cm (3 inch) gap. Dry tensile is performed on theprepared strips. Hot/Wet tensile strength testing was performed aftersoaking strips for 10 minutes in 85° C. water and then testingimmediately after removal of the strips, while they were still wet.Hot/Dry tensile testing was performed on the prepared strips using anInstron 4201 tensile tester manufactured by Instron, headquartered inNorwood, Mass.) equipped with a 1 kN load cell and an oven chamberencasing the jaws with a temperature range capability of −100 to 400° F.(−73° C. to 204° C.). The oven chamber of the tensile tester waspre-heated to 302° F. (150° C.) prior to testing. Once pre-heated, thestrips were placed in the jaws and the oven chamber was closed andequilibrated back to 302° F. (150° C.). The samples were then pulledapart at a crosshead speed of 2.54 cm/min (1 inch/min) with a 7.6 cm (3inch) gap. All tensile values are reported in Newtons (N).

Elmendorf Tear Strength Testing

Elmendorf tear strength is determined on cut samples of dried/curedhandsheet which are 6.4 cm by 7.6 cm (2.5 inches by 3 inches). A singleply sample is placed in a Thwing-Albert Tear Tester with a 1600 g teararm. The sample is notched with a 1.9 cm (0.75 inch) cut and the arm isreleased. The tear strength is recorded in grams (grams force).

Example 12 Rapid Screening Test Method

Binder formulations were rapid tested by applying to pre-formed glassfiber mats (Dura-Glass® Unbonded HEC Mat 3/4K117 from Johns Manville).The binder is made up to bath solids, typically 8%-13%, and poured in astainless steel tray; the pre-formed glass fiber mat is cut into a sheetmeasuring 28 cm by 33 cm (11″ by 13″). The pre-formed mat is thenimmersed in the binder bath just under the surface until completelywetted with the binder. The soaked mat is then transferred to the vacuumstation and the excess binder vacuumed in a similar manner to handsheets described earlier. The mat is then cured and tested as describedin the hand sheet preparation method described previously.

Only the compositions and data presented in Tables 2 and 3 are studiedby the rapid screening test method described here. All othercompositions and data are prepared and tested as described in Example11.

Example 13 Comparison of Soy Composites by Rapid Screening Test

The samples in Tables 2 and 3 were prepared by the rapid screening testmethod of Example 12.

TABLE 2 Composition and Preparation of Binder Component of theComposites Used in Rapid Screening Test Sample No. Binder¹ Additive²Preparation³ Cure Conditions Modifier⁴ 1 Starch flour — starch cooked200° C., 3 m — 2 SU-100⁵ — — 190° C., 3 m — 3 SU-100⁵ — — 200° C., 3 m —4 FG-472X⁵ — — 200° C., 3 m — 5 Soy 7B⁶ — soy cooked 150° C., 3 m — 6Soy 7B NaOH, 10% soy cooked 150° C., 3 m — 7 Soy 7B Na₂CO₃, 27% soycooked 150° C., 3 m — 8 Soy 7B NaOH, 10% — 150° C., 3 m — 9 Soy 7B NaOH,7% soy cooked 150° C., 3 m — 10 ARBO A02⁷ — — 150° C., 3 m — 11 ARBOA02⁷ — — 165° C., 4 m — 12 ARBO S01⁷ — — 155° C., 4 m — 13 50/50 Soy7B/ARBO S01 — — 155° C., 4 m — 14 50/50 Soy 7B/ARBO A02 — — 155° C., 4 m— 15 50/50 Soy 7B/ARBO S01 — soy cooked 155° C., 4 m — 16 50/50 Soy7B/ARBO A02 — soy cooked 155° C., 4 m — 17 50/50 Soy 7B/ARBO A02 NaOHcooked together 155° C., 4 m — 18 50/50 Soy 7B/ARBO A02 — soy cooked155° C., 4 m — 19 Soy 7B NaOH soy cooked 155° C., 4 m Polym. A (20%) 2050/50 Soy 7B/ARBO A02 NaOH soy cooked 155° C., 4 m Polym. A (20%) 21ARBO A02 — — 155° C., 4 m Polym. A (40%) 22 Soy 7B NaOH soy cooked 155°C., 4 m Polym. B (20%) 23 FG-472X⁵ — — 200° C., 3 m Polym. B (10%) ¹20wt. % aqueous slurry or solution. ²Where indicated, levels are based onweight percent of solid sodium hydroxide (NaOH) or sodium carbonate(Na₂CO₃) based on dry weight of soy flour; otherwise NaOH is added toachieve slurry pH of 8.0. ³All slurries were prepared by first mixing ona benchtop mechanical stirrer at high speed to achieve a stable vortex;additionally, where indicated, “soy cooked” refers to the soy slurryfurther heated to 65° C. for 30 minutes, “cooked together” refers to allcomponents of the “Binder” (soy and lignosulfonate) mixed together thencooked together by heating to 65° C. for 30 minutes. ⁴The emulsioncopolymer, Polymer A, is EA/MMA/(5% or less) of MOA, and Polymer B isMMA/(5% or less) of MOA and MAA. The amount of copolymer modifier isshown (in parentheses) as a weight percentage of polymer solids based onthe combined soy/copolymer binder solids. ⁵SU-100 and FG-472X arecommercial urea-formaldehyde (UF) resin binders available from HexionSpecialty Chemicals, Columbus, OH, USA. ⁶Soy 7B is Nutrisoy 7B, adefatted soy flour (supplied as 135 micron, equivalent to 100 mesh;80-90 PDI), available from Archer Daniels Midland Company (Decatur,Illinois, USA), further rotapped through 43 micron (325 mesh) beforeuse. ⁷Lignosulfonates ARBO A02 and ARBO S01 are the ammonium salt andsodium salts of lignosulfonate, respectively, obtained from Tembec(Temiscaming, Quebec, Canada).

TABLE 3 Tear Strength and Tensile Strength for Composite Samples 1-23prepared by Rapid Screening Method Sample Tear Dry No. Binder/Modifier¹Strength² (g) Tensile² (N) LOI 1 Starch flour 250 93.4 23% 2 SU-100 220103.6  20% 3 SU-100 215 99.2 24% 4 FG-472X 214 98.3 24% 5 Soy 7B 43652.5 18% 6 Soy 7B 384 95.6 22% 7 Soy 7B 383 49.4 25% 8 Soy 7B 334 83.619% 9 Soy 7B 386 104.1  22% 10 ARBO A02 297 30.7 19% 11 ARBO A02 23827.1 19% 12 ARBO S01 329 44.9 17% 13 50/50 Soy 7B/ARBO S01 430 59.6 20%14 50/50 Soy 7B/ARBO A02 391 64.1 24% 15 50/50 Soy 7B/ARBO S01 383 67.222% 16 50/50 Soy 7B/ARBO A02 371 67.6 23% 17 50/50 Soy 7B/ARBO A02 24646.3 21% 18 50/50 Soy 7B/ARBO A02 295 44.0 18% 19 Soy 7B/Polym. A 362(282) 126.8 (98.8) 27% 20 Soy 7B/ARBO 378 56.9 18% A02/Polym. A 21 ARBOA02/Polym. A 280 43.1 14% 22 Soy 7B/Polym. B 282 (191) 117.0 (79.2) 31%23 FG-472X/Polym. B 172 117.4  25% ¹The binder/modifier notations, andthe additive, preparation and cure conditions, are the same as in Table2. ²Tear and tensile data in parentheses indicate the experimentalnumber normalized to the target LOI of 21%.

Composite Samples 1-3 (Table 2) illustrate that commercial UF resins,SU-100 and FG-472X, show similar tear and dry tensile properties whenused as binders in glass mat composites, comparable to propertiesattained using starch flour as the binder.

Sample 5 (Soy 7B) demonstrates that the use of Soy 7B in the binder cansignificantly boost the tear strength of the composite (approximatelydouble), but with significant loss in dry tensile strength (see sample5: approximately half the tensile strength of samples 1-4). Sample 6shows that loss in tensile strength is essentially recovered, and mostof the tear strength retained, if the Soy 7B is neutralized with sodiumhydroxide (e.g. Sample 6). Neutralization with sodium carbonate,however, is ineffective in recovering the loss in dry tensile strength(Sample 7).

Samples 10-12 show that composites in which lignosulfonate is the solebinder have generally low tensile strength. The use of 50/50soy:lignosulfonate binders is explored in Samples 13-18. Although goodtear strength results from this combination, the dry tensile strength islacking compared to composites comprising current commercial UF resinbinders.

Samples 19-23 show the use of an emulsion copolymer added as a minorcomponent of the binder in soy and lignosulfonate binder systems. Thedata indicate that acrylic emulsion copolymers can be used as a bindermodifier in these systems to obtain a favorable balance of properties.

Example 14 Mechanical Properties of Soy Composites on Glass Mat

This example, and the data in Tables 4-9, follows the procedure ofExample 11.

TABLE 4 Mechanical Properties of Soy Composites Tear Tensile SampleBinder ¹ Preparation ² Modifier (g) (N) LOI 1 70 PDI ¹ Ball milled 24 hr³ — 742 66.7 18% 2 Soy 7B ⁴ Ball milled 5 hr — 670 64.1 20% 3 Soy 7BBall milled 5 hr Ex. 1 + TEA ⁵ 764 101.0 21% 4 Soy 7B Ball milled 5 hrSBR ⁶ 827 127.2 22% ¹ Prolia ™ 200/70 (defatted soy flour supplied as200 mesh (74 micron) and PDI of 70 from Cargill, Inc., Minneapolis, MN),ball milled to obtain particle size of 325 (43 micron) mesh. ² Hammermilled samples of 1-4 did not make useable mats (the add-on, or LOI, istoo high, and moreover, streaking occurs on the sheets due to clumpedparticles in the soy dispersion). Ball milling to provide a soydispersion with low enough particle size to make suitable handsheetcomposites (with no streaks). ³ In sample 1, the 70 PDI ball milledsample had to be ground on the Cowles high shear mixer to break upclumps. ⁴ Nutrisoy 7B, a defatted soy flour (135 micron (100 mesh);80-90 PDI), available from Archer Daniels Midland Company (Decatur, IL),ball milled to 43 micron (325 mesh). ⁵ Emulsion copolymer described inExample 1, at 20 wt. % of the combined soy/copolymer binder solids,additionally contains 0.65 equivalents, based on acid content of theemulsion copolymer, of triethanolamine (TEA) as a crosslinker. ⁶ Acommercial styrene-butadiene resin, Dow 6620, from Dow Chemical Company(Midland, MI),

As shown in Table 4, above (Samples 1 and 2), in the absence of emulsioncopolymer modifier, the two sources of soy do not result in appreciabledifferences in tear strength and dry tensile strength of the composite.Notably, the tensile strength is deficient in both samples. Thecopolymer modifier, added such that it is present in the amount of 20%of the solids of the combined soy/copolymer binder solids, greatlyimproves the dry tensile strength of the resulting composite (Samples 3and 4). Comparison of Samples 2 and 3 (or 2 and 4) thus shows that theemulsion polymer can significantly improve the properties of the soybinder in glass composite mats.

TABLE 5 Effect of Glycerol as Crosslinker on Mechanical Properties ofSoy Composites Tear ⁴ Tensile ⁴ Sample Binder ¹ pH ² Modifier ³ (g) (N)LOI 1 70 PDI 6.7 — 535 (509) 60.9 (58.1) 22% 2 70 PDI 6.7 2% Glycerol569 (502) 65.4 (57.2) 24% 3 70 PDI 6.7 Ex. 1 877 (705) 142.8 (115.3) 26%4 70 PDI 6.7 Ex. 1 + 1 eq Glycerol 800 (696) 124.1 (108.6) 24% 5 70 PDI6.7 Ex. 1 + 0.5 eq Glycerol 935 (818) 107.2 (93.8)  24% 6 70 PDI 8.0 —841 (729) 100.5 (88.0)  24% 7 70 PDI 8.0 — 756 (742) 85.0 (85.0) 21% 870 PDI 8.0 2% Glycerol 780 (745) 100.1 (95.5)  22% 9 70 PDI 8.0 Ex. 1910 (896) 96.5 (96.5) 21% 10 70 PDI 8.0 Ex. 1 + 1 eq Glycerol 628 (610)75.2 (71.8) 22% ¹ The soy flour is Prolia ™ 200/70 (see Table 4,footnote 1). ² In samples 1-5 the binder pH is 6.7. Samples 6-10 wereadjusted to a pH of 8.0 using sodium hydroxide solution. ³ The modifierfrom Ex. 1 is added at 20 wt. % of the combined soy/copolymer bindersolids. In Samples 4, 5, and 10, the amount of glycerol added is thenumber of equivalents based on equivalents of acid in the emulsioncopolymer. Samples 2 and 8 are non-latex containing controls for Samples4, 5, and 10, wherein, the amount of glycerol is 2% solids on totalslurry solids, which is an equal solid weight amount to that used in thelatex-containing samples. ⁴ Tear and tensile data in parenthesesindicate the experimental number normalized to the target LOI of 21%.

The experimentally obtained LOI varies slightly in Table 5, such asbetween the data obtained at pH 6.7 and that obtained at pH 8.0. Datanormalized to be equivalent to the target LOI of 21% (i.e. comparingequal binder add-on), shows that the addition of glycerol as acrosslinker, at either pH, has very little effect on the mechanicalproperties for the composites for which soy is the sole binder, and mayeven detract from tensile strength in the composites comprising thesoy/copolymer binder system.

As shown in Table 5 (comparison of Samples 6 and 7 vs. Sample 1), higherpH has a positive effect on the mechanical properties of composites forwhich soy is the sole binder, but again detracts from tensile strengthin the composites comprising the soy/copolymer binder system (compareSample 9 vs. Sample 3).

TABLE 6 Effect of Soy Flour PDI and Slurry Processing on MechanicalProperties of Soy Composites Soy Tear Tensile Sample Binder ¹ ProcessingModifier (g) (N) LOI 1 20 PDI — — 732 78.3 22% 2 20 PDI — Ex. 2 786 92.520% 3 20 PDI — Ex. 1 771 93.9 19% 4 20 PDI NaHSO₃/NaOH ² Ex. 1 767 88.520% 5 70 PDI — Ex. 7 718 91.2 20% 6 70 PDI NaHSO₃/NaOH ² Ex. 1 718 86.321% 7 90 PDI — Ex. 1 885 85.9 22% 8 90 PDI NaHSO₃/NaOH ² Ex. 1 1009 99.219% ¹ The soy flours are defatted soy flours, supplied as 74 micronparticle size (200 mesh) in Samples 1-6 and 135 micron (100 mesh) inSamples 7-8, and then ball milled to 43 micron particle size (325 mesh).² Heating soy material at 50° C. for 1 hour with sodium bisulfite(NaHSO₃) and sodium hydroxide (Na OH) as described in Example 10.

Table 6 shows that the soy/copolymer binder can produce compositematerials regardless of the PDI of the starting defatted soy flour. Thelatter was ball milled, as described above. As shown in Sample 8, forease of processing, the soy can be cooked with sodium bisulfate, whichresults in improved tear strength and tensile strength.

TABLE 7 Mechanical Properties of Copolymer Modified Soy Composites SoyTear Tensile Sample Binder Processing Modifier (g) (N) LOI 1 SU-100 ¹ —— 511 129.9 18% 2 90 PDI/325 ² NaHSO₃/ Ex. 3 ⁴ 1182 103.6 17% NaOH ³ ¹Commercial UF resin - see Table 2, footnote 5. ² 90PDI/325 is defattedsoy flour Prolia ™ 90 flakes milled to 43 micron (325 mesh). ³ The soywas heated at 50° C. for 1 hour with sodium bisulfite and sodiumhydroxide as described earlier. ⁴ The emulsion copolymer modifier isdescribed in Example 3.

Table 7 shows the mechanical properties for a preferred embodiment of acomposite of the invention and is compared to a control compositecomprising a commercial UF resin as the binder.

TABLE 8 Effect of Copolymer Modifier on Mechanical Properties of SoyComposites Sample Binder Modifier Tear (g) Tensile (N) LOI 1 FG-705¹ —454 151.2 24% 2 FG-705¹ 5% Polym. B² 656 142.3 21% 3 20 PDI³ — 535 62.322% 4 20 PDI³ 20% Ex. 1 877 142.3 26% ¹Commercial UF resin binder,pre-modified with a latex emulsion copolymer, available from HexionSpecialty Chemicals, Columbus, OH, USA. ²The emulsion copolymermodifier, Polymer B (see Table 2, footnote 4), is added to the UF resinsuch that the copolymer is 5 wt. % of the combined UF/copolymer bindersolids. ³The soy flour is Prolia 200/20 (used as 43 micron mesh particlesize, 325 mesh, as described above in Table 6, Footnote 1).

Sample 4 (Table 8) shows that composites comprising the modified soybinder can achieve a desirable property balance. Compared to the controlcomposites comprising the UF resin, Sample 4 displays far superior tearstrength, while approximately matching the tensile strength. Althoughthe binder add-on is marginally high for sample 4 (also sample 1, thecontrol), it is clear that the inventive composites provide desirablecomposites comparable to UF composites.

TABLE 9 Effect of Polymer Modifier Composition on Mechanical Propertiesof Soy Composites Sample Binder¹ Modifier² Tear (g) Tensile (N) LOI 1 90PDI Ex. 7 850 135.7 20% 2 90 PDI Ex. 4 950 149.0 21% 3 90 PDI Ex. 3 825149.0 20% 4 70 PDI Ex. 7 1027 131.2 18% 5 70 PDI Ex. 5 811 109.9 20% 670 PDI Ex. 6 936 118.8 18% 7 70 PDI 75% Ex. 5/ 657 110.3 19% 25% Aquaset1734³ 8 SU-100⁴ — 498 154.3 23% ¹The soy flours are described above(Table 6); ²The emulsion copolymer modifiers are described in Examples3-7. ³Commercial water soluble polyacrylic acid thermoset resinavailable from Rohm and Haas Company (Philadelphia, PA). ⁴SU-100 is acommercial UF resin described above (Table 2, Footnote 5).

The composites of Table 9 illustrate some preferred embodiments of theinvention. The inventive compositions provide inexpensive compositesthat retain both flexibility and strength after cure. Compared to thecontrol composites comprising the UF resin, Samples 1-4 display farsuperior tear strength, while approximately matching the tensilestrength, thereby offering a more environmentally friendly product witha desirable property balance.

Example 15 Soy Composites from Aqueous Soy Compositions ComprisingReducing Sugar

Aqueous soy compositions were prepared as shown in Table 10, below, toassess the effect on mechanical properties of added reducing sugar inthe polymer-modified soy composites on glass mat. In Table 10, the latexpolymers (prepared by the method described for Examples 1-6) have thefollowing compositions:

-   -   Latex A: 60.2 BA/23.8 STY/15 AA/1 ALMA. Tg=0° C.; 44.2% solids.    -   Latex B: 60.2 BA/35.8 STY/3 AA/1 ALMA. Tg=3.3° C.; 46.3% solids.    -   Latex C, 60.2 BA/36.8 STY/3 AA. Tg=2.9° C.; 45.8% solids.    -   Latex D: 52.3 BA/32.7 STY/15 AA. Tg=11.0° C.; 46.6% solids.

TABLE 10 Composition of Binder Component of Soy Composites ComprisingReducing Sugar ¹ Soy Latex ² Sugar ³ Ammonium Glycerol Sample (g) Latex(g) (g) Sulfate (g) (g) 1 100 A 56.6  0.0 0.0 0.0 2 100 A 56.6  0.0 0.011.1 3 100 A 56.6  0.0 4.3 0.0 4 100 A 56.6  0.0 4.3 5.0 5 100 A 56.6 5.3 0.0 0.0 6 100 A 56.6  5.3 4.3 0.0 7 100 A 56.6   11.1 ³ 4.3 5.0 8100 A 56.6 11.1 4.3 5.0 9 100 A 56.6 11.1 4.3 0.0 10 100 D 53.6 11.1 4.30.0 11 100 A 56.6 11.1 4.3 0.0 12 100 C 54.6 11.1 4.3 0.0 13 100 B 54.011.1 4.3 0.0 ¹ Approximately 240 g of DI water was added to eachformulation so that the binder solids are approximately 35%. Pamolyn 200(linoleic acid, 0.76 g) was added to all of the formulations andfunctions as a defoamer. The defatted soy flour was milled to obtainparticle size of 325 (43 micron) mesh and the formulation componentswere directly admixed using a benchtop disperser. Sodium bisulfite (1.0g) was added to all formulations except for sample 11. ² The latex ispresent at 20 wt. % of polymer solids as a percentage of the combinedpolymer and soy solids. ³ Where present in the formulation, the sugar isdextrose, except for sample 7, which uses fructose.

The glass mat preparation and test procedures for the mechanicalproperties follow the methods in Example 11. The results are shown inTable 11, below.

TABLE 11 Mechanical Properties of Soy Composites Comprising ReducingSugar ¹ Sugar Amm. Glycerol Tear Tensile Hot-Dry Hot-Wet Sample (%) ²Sulfate (%) ² (%) ² (g) (N) Tensile (N) Tensile (N) 1 — — — 927 119.368.7 29.1 2 — — 10%  1015 151.2 93.0 42.7 3 — 4% — 858 166.6 117.6 56.64 — 4% 5% 1009 161.2 129.0 71.6 5  5% — — 1041 144.7 127.8 56.6 6  5% 4%— 912 155.9 110.0 72.1 7 10% 4% 5% 964 166.6 139.3 69.2 8 10% 4% 5% 970151.8 118.0 66.5 9 10% 4% — 950 156.2 113.0 95.2 10 10% 4% — 962 155.7112.5 80.5 11 10% 4% — 1226 162.8 129.9 73.4 12 10% 4% — 900 142.8 101.982.3 13 10% 4% — 731 171.5 120.1 85.9 ¹ Binder add-on was 20% LOI +/−2%. The tensile data is normalized for 20% LOI. ² The % of additive isshown as the weight of the additive component as a percentage of thecombined weight of the soy and the additive component.

Soy compositions often fail to provide a useful level of performance inhot-wet tensile tests, as shown by sample 1 (a hot-wet tensile ofapprox. 29 N), which does not comprise a reducing sugar, or glycerol, ora thermally generated acid source, such as ammonium sulfate. Theaddition of glycerol as a sole additive has only a small effect onhot-wet tensile strength (sample 2; approx. 43 N), whereas the additionof ammonium sulfate has a larger advantageous effect on hot-wet tensilestrength (sample 3; approx. 57 N), and the combination of the two showsa further significant improvement (sample 4, comprising both glyceroland ammonium sulfate; hot-wet tensile of approx. 72 N). Addition of areducing sugar (sample 5; hot-wet tensile strength of approx. 57 N) issimilarly advantageous to the effect of ammonium sulfate, and, again,the combination of the two (sample 6, comprising both dextrose andammonium sulfate; approx. 72 N) is particularly advantageous inproviding good hot-wet tensile strength. Samples 9-13 show that theproperty balance of the inventive soy composites may be optimized byexploring variables in the latex polymer composition. Sample 9, whichexcludes sodium bisulfite in the formulation, demonstrates that sodiumbisulfite is not an essential component for property development; it isadded for ease of handling (providing viscosity reduction).

The inventive soy composites show a good balance of mechanicalproperties, including significantly improved hot-dry tensile strength,and, especially, greatly improved wet-tensile strength.

Example 16 Soy Composites from Aqueous Soy Compositions Comprising anAmino Resin

Aqueous soy compositions were prepared as shown in Tables 12 and 13,below, to assess the effect on hot-dry tensile properties for glass matcomposites of compositions resulting from the cold-blend addition ofamino resin in the polymer-modified soy binder. In Table 12, the latexpolymer A is the same latex polymer A as presented in Table 10 (preparedby the method described for Examples 1-6) with the followingcomposition:

-   -   Latex A: 60.2 BA/23.8 STY/15 AA/1 ALMA. Tg=0° C.; 44.2% solids.

The soy compositions comprising an amino resin were formulated using twomasterbatches of a soy binder, soy masterbatch (i) and soy masterbatch(ii). The masterbatches were made up as shown in Table 12, below.

TABLE 12 Composition of Soy Masterbatches ¹ Acusol Pamolyn MasterbatchSoy Latex A ² NaBS ³ Sugar ⁴ 420N 200 Sample (g) (g) (g) (g) (g) (g) (i)150.0 84.8 1.5 8.2 3.1 0.75 (ii) 150.0 84.8 1.5 0.0 3.1 0.75 ¹ DI waterwas added to each formulation so that the binder solids in themasterbatches are approximately 33%. This required the addition of 350.0g and 339.0 g of DI water in masterbatch (i) and masterbatch (ii),respectively. Pamolyn 200 (linoleic acid) functions as a defoamer.Acusol 420N is 49% solids. The defatted soy flour was milled to obtainparticle size of 325 (43 micron) mesh and the formulation componentswere directly admixed using a benchtop disperser. ² The latex (44.2%solids) is present at 20 wt. % of polymer solids as a percentage of thecombined polymer and soy solids. ³ NaBS is sodium bisulfite (100%solids). ⁴ The sugar is dextrose (100% solids).

The two masterbatch binder compositions differ only in that masterbatch(i) comprises a reducing sugar, but masterbatch (ii) does not. The soymasterbatch binders were cold blended with commercial amino resin asshown in Table 13, below.

TABLE 13 Cold Blend Formulations for Blends of Soy Masterbatch Binderand Amino Resin¹ Soy Masterbatch SU-100 FG-705 DI Water Sample (g) (g)(g) (g) 1 336.6 (i) 0.0 0.0 463.4 2 345.7 (i) 7.6 0.0 443.4 3 306.6 (i)42.7 0.0 448.4 4 219.4 (i) 88.1 0.0 479.1 5 369.7 (i) 0.0 8.1 421.4 6306.6 (i) 0.0 42.7 448.4 7 219.4 (i) 0.0 88.1 786.6 8  221.1 (ii) 91.70.0 487.3 ¹The amount of DI water was adjusted for each blend to resultin a total solids level to give approximately equal add-on (20% LOI)upon application to the fiberglass mat substrate. SU-100 and FG-705 areboth commercial urea-formaldehyde (UF) resin binders, supplied at 60%solids, available from Hexion Specialty Chemicals, Columbus, OH, USA.FG-705 is supplied as a pre-modified UF resin, modified with a latexemulsion copolymer.

The glass mat preparation and hot-dry tensile test procedures follow themethods in Example 11. The results are shown in Table 14, below.

TABLE 14 Hot-Dry Tensile Properties of Composites From UF-modified SoyCompositions¹ % UF Hot-Dry Tensile Sample Resin UF Resin (N) 1 0% —105.2 2 5% SU-100 133.5 3 25% SU-100 110.0 4 49% SU-100 135.7 5 5%FG-705 109.8 6 25% FG-705 127.8 7 49% FG-705 142.9 8 49% SU-100 138.7¹Compositions are prepared as shown in Table 13, by blending the amountand type of UF resin shown with the soy masterbatch binder (i), exceptfor sample 8, for which the UF resin was blended with the soymasterbatch binder (ii). The % UF resin is the weight percent of UFresin solids on soy masterbatch binder solids.

The data show that the hot-dry tensile strength of the composites formedfrom polymer modified soy compositions can be increased by the additionof a small amount of UF resin. The improvement is similar whether or notthe polymer modified soy composition comprises a reducing sugar.

1. A composite comprising a random collection of glass or polyesterfibers impregnated with an aqueous binder that includes a) 2 to 45weight percent, based on the weight of total binder, of an emulsion(co)polymer; b) 35 to 95 weight percent, based on the weight of totalbinder, of defatted soy flour having a particle size of not greater than43 μm; and c) 1 to 49 weight percent, based on the weight of the totalbinder, of an amino resin.
 2. The composite of claim 1 wherein theemulsion (co)polymer includes carboxylic acid groups or anhydride groupsand the amino resin is a urea formaldehyde resin.
 3. The composite ofclaim 2 wherein the emulsion (co)polymer includes, as polymerized units,from 0.1 to 5 weight percent, based on the weight of the polymer, of oneor more multi-ethylenically unsaturated monomers.
 4. The composite ofclaim 3 in which the aqueous binder further includes one or morereducing sugars.
 5. The composite of claim 3 wherein themulti-ethylenically unsaturated monomer is allylmethacrylate.
 6. Thecomposite of claim 1 wherein the defatted soy flour is denatured.
 7. Thecomposite of claim 4 wherein the reducing sugar is selected from thegroup consisting of fructose, glyceraldehydes, lactose, arabinose,maltose, glucose, dextrose, xylose, and levulose.
 8. The composite ofclaim 1 wherein the aqueous binder further comprises sodium bisulfite orsodium metabisulfite.
 9. The composite of claim 1 wherein the aqueousbinder further comprises one or more ammonium salts of an inorganicacid.
 10. The composite of any of claim 1 which is cured.
 11. A methodfor producing the composite of claim 1 comprising: a) treating a randomcollection of glass or polyester fibers with an aqueous binder thatincludes i) one emulsion polymer; ii) 35 to 95 weight percent, based onthe weight of total binder, of defatted soy flour having a particle sizeof not greater than 43 μm; and iii) 1 to 49 weight percent, based on theweight of the total binder, of a urea formaldehyde resin; and b)removing excess binder from the substrate.
 12. The method of claim 11which further includes after step b) the step of curing or drying thebinder on the random collection of glass or polyester fibers.
 13. Themethod of claim 1.1 wherein the binder further includes one or morereducing sugars selected from the group consisting of fructose,glyceraldehydes, lactose, arabinose, maltose, glucose, dextrose andlevulose.
 14. A composite comprising a random collection of glass orpolyester fibers impregnated with an aqueous binder that includes a) 10to 20 weight percent, based on the weight of total binder of astyrene-acrylic polycarboxy emulsion copolymer crosslinked with allylmethacrylate; b) 60 to 75 weight percent, based on the weight of totalbinder, of defatted soy flour having a particle size of not greater than43 μm; c) 5 to 20 weight percent, based on the weight of the totalbinder, of a urea formaldehyde resin; d) 2 to 10 weight percent, basedon the weight of the total binder, of dextrose; and e) 0.1 to 1 weightpercent, based on the weight of the total binder, of sodium bisulfite orsodium metabisulfite.
 15. The composite of claim 14 which is cured.